US2032612A - Solid seasoning composition containing lecithin - Google Patents

Description

Patented Mar. 3, 1936 SOLID SEASDNING COMPOSITION CONTAINING LECITHIN Carroll L. Griffith and Lloyd A. Hall, Chicago, 111., assignors to The Griflith Laboratories, Inc., Chicago, Ill., a corporation of Illinois No Drawing. Application June 16, 1934,

. Serial No. 730,911

13 Claims. (Cl. 9911) The present invention relates to a flavoring composition containing oleo-resin of capsicum and a chloride of an alkali metal. It has particular reference to a solid composition in which there are crystals of a chloride salt, with or without other solid particles, as a vehicle, or base, or carrier, for oleo-resin of capsicum with or without other flavoring materials, particularly essential oils.

in In flavoring meats for use in sausages, frankfurters, bologna, meat-loaf and the like, it is customary to use prepared seasonings which are derived from the natural substances, but which are devoid of fiber from the natural sources. Essential oils, extracts, oleo-resins, and like substances are compounded with a suitable solid carrier, to form a bulky granular mass compounded specially with reference to certain formulas. Sugar is a common vehicle for such a carrier. Salt is desirzo able, but in some instances it is avoided as will hereinafter appear. Sugar may create too much sweetness. Salt alone, or mixtures of salt and sugar, or salt and other substance may be. used in certain cases. However, when oleo-resin of 5 capsicum is present, sodium chloride is undesirable. The combination without a suitable correcting agent leads to a slow bleaching out of the color of the capsicum. Bleaching occurs in the absence of essential oils, but it is even greater 30 when essential oils are present. The present invention applies a. corrective agent permitting use of various combinations without the undesirable bleaching.

Oleo-resin of capsicum on exposure to air has 2:5 an increasing acid content. It is apparently a condition caused by oxidation in which acid substance is formed. Such capsicum has a charac teristic red-orange color by which its presence is indicated to the eye. This color has a valuable function of indicating to the trade the use of natural capsicum substance, and of capsicum in oleo-resin form.

Functionally, salt in the vehicle may be used. But commercially, where a seasoning ingredient 1' having sodium chloride and a colored oleo-resin of capsicum is an item of commerce, there are conditions which bar such mixtures from successful use in trade. A composition containing sodium chloride and colored oleo-resi-n of capsicum so is originally of a uniform capsicum color. on standing for several months the color bleaches out. The bleaching is first noticeable in about three weeks. The parts most exposed to air bleach first, and faster, thus giving an appearance of great'change, and. 01 irregular change.

The product may be mottled in various shades oi color from the original capsicum color to a highly bleached capsicum color. All these changes create in the mind of the user a prejudice to the material. Complaints of spoilage may arise. The user is fearful of loss of strength and hence in fear that he cannot make a standard meat prodon. Alcohols such as borneol and linalol are found in oil of coriander. N-decylic aldehyde occurs also on oil of coriander.

The present invention is based upon the discovery that acid in the oleo-resin of capsicum, or

in other oleo-resins, or in other oils or materials which are present originally when the seasoning composition is made, or acids which may be later formed, have a certain action in the presence of chloride salt, to form some active substance capable of bleaching the color imparted to the seasoning composition by the original oleo-resin of capsicum. The intermediate reactions involved are not fully comprehended, nor are they material. On the basis that it occurs in the presence of acid coupled with the presence of a chloride salt and of oleo-resin of capsicum to produce a bleaching condition evidenced by change in appearance, the present invention aims to overcome this condition by adding a suitable corrective agent which prevents the bleaching, and hence the change in appearance.

In our copending applications Serial No. 730,- 908, filed June 16, 1934; Serial No. 730,909, filed June 16, 1934; and Serial No. 730,910, filed June 16, 1934, which have matured into Patents Number 1,995,119, 1,995,120 and 1,995,121 respectively, issued March 19, 1935, it has been shown that various types of corrective agents may be added to retard or prevent the bleaching. Additions of mineral alkali or of organic amines are ways to minimize bleaching, by neutralizing the causative acidity. Still another way is by bufling the causative acidity with a suitable bufier salt such as salts of strong bases and weak acids, particularly sodium citrate, and potassium tartrate.

In these methods of correcting to minimize bleaching, the causative acid is no doubt produced by exposure of the mass to oxygen of the air.

The present invention is directed to use of an gent to be added to retard the oxidation eflfect, so that the conditions tending to produce bleaching do not arise so fast. It has been discovered that lecithin has the property of retarding oxidation in the compositions with which this invention is concerned. It is particularly to be noted that lecithin alone is not effective to prevent bleaching, became it appears only to be a retardent of oxidation. However, when it is used with any one of the other agents referred to, it is very effective. Its use in combination with such other agents permits using less of the agent, to produce a given stability, or it prolongs the period of stability which is imparted by a given quantity of the other agent. In other words where the corrective agents of the said prior applications apparently serve to remove the harmful effects of oxidation, the lecithin alone in small quantities is inadequate as an antibleaching agent, yet it is quite effective when used in combination with the corrective agent. Its eifect is therefore more than additive to the effect of the corrective agent.

In accordance with the law of mass action the removal of a product of a given reaction tends to speed up that reaction. Therefore, if neutralizing agents for acid are employed it appears that the oxidation might proceed more rapidly. However, this is not effective to produce the bleaching because the oxidation product is altered. The lecithin acts on the formative side of the oxidation reaction by tending to slow it down, hence giving less product to beremoved from the other side. As a result less of the corrective agent may be employed. As a result of the slowing down of' oxidation the composition remains more nearly in its original form, and therefore it is more stable and is practically nonbleaching. The lecithin therefore may be considered as a stabilizing agent whereas the other material is considered as a corrective agent.

It is therefore an object of the present invention to add a stabilizing agent to a solid seasoning composition of the character described which is subject to self-bleaching as a result of slow oxidation.

A particular object of the invention is to add to such a composition an anti-oxidant.

A further object of the invention is to add lecithin to such a seasoning composition.

Still another object of the invention is to produce a practically non-bleaching seasoning composition of the character described by using a combination of a stabilizing agent which retards oxidation, with a corrective agent which alters the active harmful product of oxidation before it may adversely act to generate bleaching conditions.

It is another object of the invention to make a solid flavoring composition containing oleoresin of capsicum and sodium chloride particles which are specially produced in special powderlike microscopically crystalline form, as the whole or as part of the solid base for flavoring ingredients.

Various other and ancillary objects and advantages of the invention will become apparent from the following description and explanation of the invention.

As stated heretofore three classes of corrective agents have been set forth as suitable to render the products of oxidation inactive. These are (1) mineral alkalis, either soluble or insoluble, (2) organic amines, and (3) buffer salts, that is, salts of strong bases and of weak organic acids.

In using an inorganic base, numerous metals are available which are not harmful in foods in the quantities needed. Sodium, lithium, potassium, magnesium and calcium are the most common suitable ones, but this list is not an exclusi\e one. The oxides, carbonates, hydroxides and bcarbonates are common forms for these metals .for such uses. Commonly the alkali metals, Sulh as potassium and sodium are used as carbonatesor as bicarbon-ates, because the oxides and hydroxides are too powerful as lyes to warrant safety in using them, as is well known. Magnesium and calcium may be used also in a carbonate form, but preferably the oxides or hydroxides of each may be used, or even the mixed or complex oxides or hydroxides containing both magnesium and calcium may be employed.

In organic bases of the character described unite with the acid initially present, or formed, either in the oleo-resins or oils, or as a result of action of such acids on the chloride.

In using an organic alkali numerous organic amines are available which are not harmful in I foods in the quantities employed. The ethanol amines,such as mono-,di-, and tri-ethanolamines are the most common suitable ones, but this list is not an exclusive one.

Organic bases of the character described counif teract the acid initially present, or formed, either in the oleo-resins or oils, or as a result of action of such acids on the chloride. Amines also have the power of uniting with phenols and aldehydes.

Whether or not the amines in the present inven- 1 tion unite with or tend to unite with aldehydes and phenols which may be present is not known. However, it is known that the amine is effective to prevent the creation of bleaching conditions.

It is also possible that the tendency to unite with phenols and aldehydes renders the amine a sort of fixing agent to fix the certain volatile ingredients in the composition. The amines are derivatives of ammonia and even though three organic radicals are attached to the nitrogen of the ammonia molecule, the so substituted molecule still has the power of uniting with acids to form salts, such as triethanol amine borate, acetate, chloride, etc. In the present invention it functions to form a salt of what free acid is available. Where the amine may be combined with other active ingredients, the union may be broken up by action of the acid, thereby to release the amine for union with the acid and to release the said active in-- gredients for normal use.

Herein, where the-term triethanolamine is referred to, the commercial material of that designation is meant. This is not the pure tertiary amine, but is amixture which also contains some diethanolamine, and some monoethanolamine. A typical average analysis is:

Per cent Triethanolamine -75 Diethanolamine 20-25 Monoethanolamine 0 5 'lithium, ammonium, potassium, magnesium and calcium are the most common suitable ones, but this list is not an exclusive one. The available acids are limited somewhat by the physiological effects. Commonly the alkali metals, such as potassium and sodium are used as the normal salts of the acids, although the acid salts may be used, or the mixed salts, such as Rochelles salts.

Salts of the character described react with the acid initially present, or formed, either in the oleo-resins or oils, or as a result of action of such acids on the chloride. The acids take the metal from the corrective salt and set free the weak organic acid. It is evident that these acids are insufficient in strength to permit bleaching conditions to arise, or that they are somehow destroyed so that an acid condition does not accumulate. These salts may function merely as sources of alkali material, but the use is distinctly different from the use of alkali materials in that the corrective agent is not strictly an alkaline one in character. By using these salts the mass may be made stable against bleaching, while having measurable acidity.

Because a chloride such as sodium chloride is herein made a new ingredient in successful seasoning compositions, some attention may advantageously be given to it. Heretofore, so far as known, such compositions of unsuccessful nature wherein sodium chloride salt has been employed have been made with sodium chloride crystals, produced by grinding of large crystals, or produced by crystallization processes from a mother brine or in other words, from ordinary commercial sodium chloride.

According to one feature of the present invention the form of the salt may be improved to give an improved character to the composition. This improvement in the mass is greatest when all or a very large proportion of base or vehicle is sodium chloride. The common crystal form of sodium chloride is first destroyed by dissolving the salt in water to form a strong brine. The brine is then subjected in subdivided form, as a spray or a thin film, to a rapid or flash evaporation process whereby new salt particles are obtained having a more beneficial form for use in the present invention.

is to make a brine of about 27% sodium chloride.

This is heated to about 180 F. and is sprayed or splashed onto hot revolving rolls or drums having a temperature of about 285 F. to 300 F. A fine powder forms on the rolls which falls off or is scraped off. The powder app ars to the eye as amorphous, but in fact it is microscopically crystalline. To the fingers it feels soft and flaky and unlike ground salt crystals. In the microscope it indicates the presence of the usual cubic crystal lattice of sodium chloride. The fine powder form provides a high specific surface for holding the seasoning ingredients, making a higher maximum safe capacity for liquid additions without settling of liquid from solid. The fine powder form also provides more spaces of capillary proportions in which liquid and semi-liquid substance may be housed.

The use of a corrective agent in the original composition makes it permissible to increase the contact area between sodium chloride and the material containing the oleo-resin of capsicum. In the absence of such corrective agent the use of the improved crystal form would only hasten the a'mdesirable bleaching action.

Of course, the invention is not limited to use oxidation to bleach the mass.

of salt made as above described. Ordinary salt grains, or ground forms of salt crystals may be used. Ordinary salt crystals may be ground in the presence of other material, preferably all of the material, which is to enter into the ultimate composition. Sugar, which is a normal seasoning ingredient, or other crystals, also may be present with or without employment of such grinding step.

In selecting salt, it is desirable to use a pure salt or one which is not so impure as to have the property of absorbing moisture from the air, or from other materials. This tends to dissolve salt and to provide a medium for easy distribution of acid or other soluble substance which is effective inbleaching. Where the salt is made into powder form by the hot rolls as above described it is desirable to let it stand exposed to the air for a suflicient length of time to'allow the salt powder to arrive at an equilibrium condition, as to moisture content. Thus caking of the ultimate mass may be prevented. However, where some residual moisture is left in the salt, or is allowed to accumulate in the salt, a suitable agent may be added which prevents undue caking.

Glycerin or corn sugar may advantageously be mixed into the salt-base mass as a protective agent to minimize any tendency to cake. Such addition is more particularly desirable where the fine powder-like particles of sodium chloride are used. When glycerin is so used, it acts as a fixative agent to dissolve volatile material and lessen loss of it by evaporation. Fixative agent other than glycerin or its equivalent such as well known edible or harmless fats and oils may be employed in place of or in combination with glycerin to secure the well known advantages of such use singly, or the use as so combined. Such functions are known in the Allen Patent No. 1,829,431,

and in the application of Carroll L. Griffith (joint applicant herein), Serial No. 519,686, filed March 2, 1931, now Patent No. 1,971,910, issued August It is not intended to indicate that the acid all necessarily, in the oleo-resin of capsicum. Other oils or other substances may be present which in themselves are sumciently acid, or which on standing in a seasoning composition may produce an acid condition sufficient to act in the presence of chloride and thereby produce the said bleachingcondition evidenced by the change of color in the oleo-resin of capsicum.

While it is not known exactly what the conditions are, it is evident that the oleo-resin of capsicum, with or without other flavoring ingredients, in the absence of chloride is not bleached. The non-bleaching action of an uncorrected mixture may be rapid or slow and becomes apparent in about three weeks. It is usually complete in a few months. It is therefore possible that a trace of chlorine is gradually released, and as it is used up to bleach, more is formed. It is also possible that the chloride, or .even hydrochloric acid, or the chlorine ion is a catalyst for an air 7 At least, it is known that the presence of a corrective agent of the kinds described is effective to prevent the bleaching. It is also known that the presence of lecithin improves the desired effect of said corrective agent, and-this is believed to be by its function of retarding oxidation.

scribed, and preferably from the salt powder or the "processed salt above described.

Example I Per cent Sodium chloride 91.88 Calcium carbonate 2.35 Lecithin 1.17 Glycerin 1.25 Cleo-resins of capsicum 2.10 Essential oils of spices 1.25

Example II Percent Sodium chloride 91.48 Magnesium oxide 2.00 Lecithin 1.17 Corn sugar 2.00 Cleo-resins of capsicum 2.10 Essential oils of spices 1.25

Example III Per cent Sodium chloride 45.94 Spray milk powder 45.94 Magnesium hydroxide 2.35 Glycerin 1.25 Lecithin 1.17 Cleo-resins of capsicum 2.10 Essential oils of spices 1.25

Example IV Per cent Sodium chloride 73.80 Corn sugar 18.43 Sodium bicarbonate 2.00 Lecithin 1.17 Glycerin 1.25 Cleo-resins of capsicum 2.10 Essential oils of spices 1.25

Example V Parts Sodium chloride 247 Sodium bicarbonate 6 Lecithin 3 Glycerin 3.2 Cleo-resins of capsicum 3.5 Olen-resin of ginger .2 Essential oils of spices 3.2

Example VI Per cent Sodium chloride 92.06 Sodium citrate 2.34 Lecithin 1.00 Glycerin 1.25 Cleo-resins of capsicum 2.10 Essential oils of spices 1.25

Example VII Per cent Sodium chloride 91.90 Sodium tartrate 2.50 Lecithin 1.00 Glycerin 1.25 Oleo-resins of capsicum 2.10 Essential oils of spices 1.25

Example VIII Per cent Sodium chloride 94.00 Commercial triethanolamine .40 Lecithin 1.00 Glycerin 1.25 Oleo-resins of capsicum 2.10 Essential oils of spices 1.25

Among the, common flavoring materials used where meats are to be-flavored are, oleo-resin of ginger, oil of coriander, oil of nutmeg, oil 0! cloves, oil of cassia, oil of allspice, oil of ginger, and yet others.

It is, of course, to be understood that the formulas may be changed in many ways without departing from the spirit and scope of the invention as set forth in the appended claims.

We claim:

1. The method of preventing a mixture containing colored oleo-resins of capsicum and solid sodium chloride from early bleaching out in re spect to the color of said oleo-resins, which comprises adding a corrective agent to prevent developed acid from effecting early bleaching, said agent being selected from the group consisting of (1) material having available alkali for neutralizing acidity, (2) material having organic amine available for neutralizing acidity, and (3) acidity bufling salt of a strong base and a weak organic acid, and adding lecithin as an anti-oxidant to retard the development of acid by oxidation.

2. A solid seasoning composition containing in combination sodium chloride, colored oleo-resins of capsicum, available alkali for neutralizing acidity whereby to avoid early bleaching of the colored oleo-resins of capsicum, and lecithin as an antioxidant to retard the development of acidity by oxidation.

3. A solid seasoning composition containing in combination sodium chloride, colored oleo-resins of capsicum, ava'lable organic amine for neutralizing acidity whereby to avoid early bleaching of the colored oleo resins of capsicum, and lecithin as an anti-oxidant to retard the development of acidity by oxidation.

4. A solid seasoning composition containing in combination sodium chloride, colored oleo-resins of capsicum, salt of a strong base and a weak organic acid which acts as a butler salt for developed acid with resulting acidity which avoids early bleaching of the oleo-resins of capsicum, and lecithin as an anti-oxidant to retard the development of acidity by oxidation.

5. A solid seasoning composition containing in combination sodium chloride, colored oleo-resins of capsicum, soluble mineral alkali for neutralizing acidity, and lecithin.

6. A solid seasoning composition containing in combination sodium chloride, colored oleo-resins of capsicum, an inorganic compound containing available metal oxide for neutralizing acidity, and lecithin.

7. A solid seasoning composition containing in;

combination sodium chloride, colored oleo-resins" of capsicum, ethanol amine for neutralizing acid ity, and lecithin.

8. A solid seasoning composition containing in combination sodium chloride, colored oleo-resins of capsicum, a normal salt of alkali metal and edible fruit acid, and lecithin.

9. In a solid seasoning composition containing the combination of sodium chloride and colored oleo-resins of capsicum, which alone is subject to oxidation and subsequent bleaching, the presence of lecithin to retard oxidation, together with a corrective agent for avoidingearly bleaching resulting from oxidation, said agent beingselected from the group consisting of 1) material having available alkali for neutralizing acidity,

(2) material having organic amine available for neutralizing acidity, and (3) acidity bufling salt of a strong base and a weak organic acid.

10. The method of preventing a mixture containing essential oils, colored oleo-resins of capsicum and solid sodium chloride from early bleaching out in respect to the color of said oleo-resins, which comprises adding a corrective agent to prevent developed acid from eiiecting early bleaching, said agent being selected from the group consisting of (1) material having available alkali i'or neutralizing acidity, (2) material having organic amine available for neutralizing acidity, and (3) acidity bufiing salt oi a strong base and a weak organic acid, and adding lecithin as an anti-oxidant to retard the development of acid by oxidation. 7

11. The method of preventing a mixture containing essential oils, fixative therefor, colored oleo-resins of capsicum and solid sodium chloride from early bleaching out in respect to the color of said oleo-resins, which comprises adding a corrective agent to prevent developed acid from eflecting early bleaching, said agent being selected from the group consisting of (1) material having available alkali i'or neutralizing acidity. (2) material having organic amine available for neutralizing acidity, and (3) acidity bufling salt of a strong base and a weak organic acid, and adding lecithin as an anti-oxidant to retard the development of acid by oxidation. I

12. In a solid seasoning composition containing the combination 01' sodium chloride, essential oils, and colored oleo-resins of capsicum which is subjected to oxidation and subsequent bleaching, the presence of lecithin to retard oxidation, together with a corrective agent for avoiding early bleaching resulting from oxidation, said agent being selected from the group consisting of (1) material having available alkali for neutralizing acidity, (2) material having organic amine available for neutralizing acidity, and (3) acidity bufling salt of a strong base and a weak organic acid.

13. In a solid seasoning composition containing the combination of sodium chloride, essential oils, fixative therefor, and colored oleo-resins of capsicum which is subjected to oxidation and subse quent bleaching, the presence of lecithin to retard oxidation, together with a corrective agent for avoiding early bleaching resulting from oxidation, said agent being selected from the group consisting of (1) material having available alkali for neutralizing acidity, (2) material having organic amine available for neutralizing acidity, and (3) acidity bufiing salt of a strong base and a weak organic acid.

' CARROLL L. GRIFFITH. LLOYD A. HALL.